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1 Interactions of organosulfates with water vapor under sub- and supersaturated 2 conditions 3 4 Chao Peng,1,2 Patricia N. Razafindrambinina,3 Kotiba A. Malek,4 Lanxiadi Chen,1,2,7 Weigang 5 Wang,5 Ru-Jin Huang,6 Yuqing Zhang,1,2 Xiang Ding,1,2 Maofa Ge,5 Xinming Wang,1,2 Akua A. 6 Asa-Awuku,3,4 and Mingjin Tang1,2,7,* 7 8 1 State Key Laboratory of Organic Geochemistry, Guangdong Key Laboratory of Environmental 9 Protection and Resources Utilization, and Guangdong-Hong Kong-Macao Joint Laboratory for 10 Environmental Pollution and Control, Guangzhou Institute of Geochemistry, Chinese Academy of 11 Sciences, Guangzhou 510640, China 12 2 CAS Center for Excellence in Deep Earth Science, Guangzhou 510640, China 13 3 Department of Chemistry and Biochemistry, College of Computer, Mathematical and Natural 14 Sciences, University of Maryland, College Park, MD 20742, USA 15 4 Department of Chemical and Biomolecular Engineering, A. James Clark School of Engineering, 16 University of Maryland, College Park, MD 20742, USA 17 5 State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Beijing National 18 Laboratory for Molecular Sciences, CAS Research/Education Center for Excellence in Molecular 19 Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China 20 6 Key Laboratory of Aerosol Chemistry and Physics, State Key Laboratory of Loess and 21 Quaternary Geology, Institute of Earth and Environment, Chinese Academy of Sciences, Xi'an 22 710061, China 1 23 7 University of Chinese Academy of Sciences, Beijing 100049, China 24 25 *Correspondence: Mingjin Tang ([email protected]) 26 27 2 28 Abstract 29 Organosulfates (OS) are important constituents of secondary organic aerosols, but their 30 hygroscopic properties and cloud condensation nucleation (CCN) activities have not been well 31 understood. In this work we employed three complementary techniques to characterize interactions 32 of several OS with water vapor under sub- and supersaturated conditions. A vapor sorption 33 analyzer was used to measure mass changes of OS samples with RH (0-90%); among the 11 34 organosulfates examined, only sodium methyl sulfate (methyl-OS), sodium ethyl sulfate (ethyl- 35 OS), sodium octyl sulfate (octyl-OS) and potassium hydroxyacetone sulfate were found to 36 deliquesce as RH increased, and their mass growth factors at 90% RH were determined to be 37 3.65±0.06, 3.58±0.02, 1.59±0.01 and 2.20±0.03. Hygroscopic growth of methyl-, ethyl- and octyl- 38 OS aerosols was also studied using a humidity tandem differential mobility analyzer (H-TDMA); 39 continuous hygroscopic growth was observed, and their growth factors at 90% RH were 40 determined to be 1.83±0.03, 1.79±0.02 and 1.21±0.02. We further investigated CCN activities of 41 methyl-, ethyl- and octyl-OS aerosols, and their single hygroscopicity parameters (κccn) were 42 determined to be 0.459±0.021, 0.397±0.010 and 0.206±0.008. For methyl- and ethyl-OS aerosols, 43 κccn values agree reasonably well with those derived from H-TDMA measurements (κgf) with 44 relative differences being <25%, whereas κccn was found to be ~2.4 times larger than κgf for octyl- 45 OS, likely due to both solubility limit and surface tension reduction. 46 3 47 1 Introduction 48 Secondary organic aerosol (SOA) contributes approximately 70% to the global atmospheric 49 organic aerosols (Hallquist et al., 2009; Jimenez et al., 2009). SOA can affect the Earth’s radiative 50 forcing and climate directly by scattering and absorbing solar and terrestrial radiation, and also 51 indirectly by acting as cloud condensation nuclei (CCN) or ice nucleating particles (Moise et al., 52 2015; Shrivastava et al., 2017). Consequently, it is important to understand the source, formation, 53 and physicochemical properties of SOA (Pöschl, 2005; Jimenez et al., 2009; Noziere et al., 2015; 54 Peng et al., 2020). However, SOA concentrations on the global scale are significantly 55 underestimated by many modeling studies (Heald et al., 2005; Kanakidou et al., 2005; Ervens et 56 al., 2011; McNeill et al., 2012; Shrivastava et al., 2017), indicating that there might exist unknown 57 while important precursors and/or formation mechanisms of SOA. 58 Organosulfates (OS), which could contribute to the total mass of ambient organic aerosols by 59 as much as 30%, may largely explain the discrepancy between observed and modeled global SOA 60 budgets (Surratt et al., 2008; Tolocka and Turpin, 2012; Liao et al., 2015). A number of field 61 measurements have observed significant amounts of OS in ambient aerosols in different regions 62 over the globe (Froyd et al., 2010; Kristensen and Glasius, 2011; He et al., 2014; Hettiyadura et 63 al., 2015; Riva et al., 2019; Wang et al., 2019a; Wang et al., 2019b; Zhang et al., 2019; 64 Bruggemann et al., 2020; Wang et al., 2020). For example, the mass concentration of sodium 65 methyl sulfate, the smallest organosulfate, was found to be 0.2-9.3 ng m-3 in Centreville, Alabama 66 (Hettiyadura et al., 2017). Hydroxyacetone sulfate, which may originate from both biogenic 67 (Surratt et al., 2008) and anthropogenic emissions (Hansen et al., 2014), has been detected at 68 various locations, such as the Arctic (1.27-9.56 ng m-3) (Hansen et al., 2014), Beijing (0.5-7.5 ng 69 m-3) (Wang et al., 2018), Shanghai (1.8-2.3 ng m-3) (Wang et al., 2021), Xi’an (0.9-2.6 ng m-3) 4 70 (Huang et al., 2018), Centreville (1.5-14.3 ng m-3) (Hettiyadura et al., 2017) and Iowa City (4.8±1.1 71 ng m-3) (Hughes and Stone, 2019). In addition, benzyl and phenyl sulfates were also ubiquitous in 72 the troposphere, with reported concentrations up to almost 1 μg m-3 (Kundu et al., 2013; Ma et al., 73 2014; Staudt et al., 2014; Huang et al., 2018). 74 As OS are ubiquitous in the troposphere, it is important to understand their hygroscopic 75 properties and CCN activities in order to assess their environmental and climatic effects 76 (Kanakidou et al., 2005; Moise et al., 2015; Tang et al., 2016; Tang et al., 2019a), especially 77 considering that OS could contribute up to 30% of total mass of organic aerosols in the troposphere 78 (Surratt et al., 2008; Tolocka and Turpin, 2012; Liao et al., 2015). However, to our knowledge, 79 only two previous studies have explored their hygroscopic properties and CCN activities (Hansen 80 et al., 2015; Estillore et al., 2016). Hansen et al. (2015) investigated hygroscopic growth and CCN 81 activation of limonene-derived OS (with molecular weight of 250 Da) and their mixtures with 82 ammonium sulfate. Hygroscopicity of pure limonene-derived OS was weak, and its hygroscopic 83 growth factors were determined to be 1.0 at 80% RH and 1.2 at 93% RH (Hansen et al., 2015). 84 Estillore et al. (2016) investigated hygroscopic growth of a series of OS, including potassium salts 85 of glycolic acid sulfate, hydroxyacetone sulfate, 4-hydroxy-2,3-epoxybutane sulfate, and 2- 86 butenediol sulfate, as well as sodium salts of benzyl sulfate, methyl sulfate, ethyl sulfate, and 87 propyl sulfate. Continuous hygroscopic growth (i.e. without obvious deliquescence) was observed 88 for these OS aerosols (Estillore et al., 2016); in addition, their hygroscopic growth factors at 85% 89 RH were determined to vary between 1.29 and 1.50, suggesting that their hygroscopicity showed 90 substantial variation. In summary, it is fair to state that hygroscopic properties and CCN activities 91 of OS have not been well understood. 5 92 In this work, three complementary techniques were used to investigate hygroscopic properties 93 and CCN activities of a series of OS, including sodium methyl sulfate, sodium ethyl sulfate, 94 sodium octyl sulfate, sodium dodecyl sulfate, potassium hydroxyacetone sulfate, potassium 3- 95 hydroxy phenyl sulfate, potassium benzyl sulfate, potassium 2-methyl benzyl sulfate, potassium 96 3-methyl benzyl sulfate, potassium 2,4-dimethyl benzyl sulfate and potassium 3,5-dimethyl benzyl 97 sulfate. A vapor sorption analyzer was employed to measure mass change of these OS samples as 98 a function of RH. In addition, hygroscopic growth (change in mobility diameters) and CCN 99 activation of submicron aerosol particles were studied for sodium methyl sulfate, sodium ethyl 100 sulfate and sodium octyl sulfate, using a humidity tandem differential mobility analyzer (H-TDMA) 101 and a cloud condensation nuclei counter (CCNc). Due to their very limited quantities, we could 102 not carry out H-TDMA and CCNc measurements for other OS samples which were synthesized 103 by us. In addition, we also investigated the impacts of sodium methyl sulfate, sodium ethyl sulfate 104 and sodium octyl sulfate on hygroscopic properties and CCN activities of ammonium sulfate. 105 2 Experimental section 106 2.1 Chemicals and reagents 107 Sodium methyl sulfate (CH3SO4Na, >98%) and sodium ethyl sulfate (C2H5SO4Na, >98%) 108 were purchased from Tokyo Chemical Industry (TCI); sodium octyl sulfate (C8H17SO4Na, >99%), 109 sodium dodecyl sulfate (C12H25SO4Na, >99%) and ammonium sulfate (>99.5%) were supplied by 110 Aldrich. The other seven OS, including potassium hydroxyacetone sulfate, potassium 3-hydroxy 111 phenyl sulfate, potassium benzyl sulfate, potassium 2-methyl benzyl sulfate, potassium 3-methyl 112 benzyl sulfate, potassium 2,4-dimethyl benzyl sulfate and potassium 3,5-dimethyl benzyl sulfate, 113 were synthesized using the method described by Huang et al. (2018), and their purities were found 6 114 to be >95% using nuclear magnetic resonance analysis. Chemical formulas and molecular 115 structures of OS investigated in this study can be found in Figure 1.

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